CN104628007B - Preparation method of mesoporous silica nanoparticles - Google Patents
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Abstract
The invention provides a preparation method of mesoporous silica nanoparticles. The method comprises the following steps: adsorbing a silicon dioxide precursor by using amino functionalized polyglycerol, then hydrolyzing, carrying out solid-liquid separation, washing, and drying to obtain the mesoporous silica nanoparticles. The method specifically comprises the following steps: dissolving tetraethoxysilane and amino functionalized polyglycerol in an organic solvent for blended adsorption; then adding ammonia water for hydrolysis reaction; and finally, carrying out solid-liquid separation on a solution after reaction, and washing and drying to obtain the mesoporous silica nanoparticles. The method is simple, free of surfactants and relatively low in preparation cost; the grain sizes of the prepared mesoporous silica nanoparticles can be controlled in a nano dimensional range of 20-50 nanometers, the mesoporous silica nanoparticles have good monodispersibility, holes of 1-2 nanometers exist in the particles, and the mesoporous silica nanoparticles have good biocompatibility and biodegradability and can be used for loading guest molecules and applied to the field of biological medicines.
Description
Technical field
The invention belongs to the preparing technical field of porous material, more particularly, to a kind of system of mesoporous silicon dioxide nano particle
Preparation Method.
Background technology
Mesoporous silicon dioxide nano particle refers to a diameter of hundreds of nanometer, and inside has the porous knot within 10 nanometers
The nano material of structure.This nano-particle is based on spherical or oval, stub type or hollow shell structure.This nano-particle
Because of Stability Analysis of Structures, good biocompatibility, and inside have abundant loose structure, thus are used frequently as medicine or other
The carrier of biomolecule is applied to biomedicine field.
Preparing the general method of mesoporous silicon dioxide nano particle at present is that Cai Qiang and victor lin et al. grows up
Surfactant mediation sol-gal process, that is, tetraethyl orthosilicate in the surfactant of high concentration (as cetyl front three
Base ammonium bromide) solution in by self assembly hydrolyze generation, then pass through high-temperature calcination or acid alcohol mixed solution remove table
Face activating agent, such as cn 1715184 discloses a kind of preparation method of sphericity mesoporous silicon dioxide material: utilizes cationic surface
Activating agent is template, is silicon source with tetraethyl orthosilicate, hydrolytic condensation forms in the basic conditions.The method is not only using substantial amounts of
Surfactant and increase cost, and use exacting terms to remove surfactant.In addition cn 102050454b
Disclose a kind of preparation method of employing Template synthesis mesoporous silicon dioxide micro-sphere, using the poly- second two of two kinds of different molecular weights
Alcohol (peg) is silicon source as mixed templates, tetraethyl orthosilicate (teos), and peg mixed templates, teos, hydrochloric acid and water are pressed
Certain proportion mix, mixed solution in 30～60 DEG C of waters bath with thermostatic control, isothermal reaction 6～20h, by product separate, obtain
Product is separated, drying and calcination aftertreatment technology, prepared mesoporous sphere silicon dioxide microsphere.But prepared by the method
Mesoporous silicon oxide particle diameter larger, and complex treatment process.
Mesoporous silicon dioxide nano particle of conventional method preparation, generally more than 100 nanometers, carries as antineoplastic
Body, in order to improve its epr effect, less than 100 nanometers of particle is more preferably, and this prepares silica dioxide nano particle for tradition
The method of son proposes bigger challenge.
Content of the invention
It is an object of the invention to provide a kind of preparation of mesoporous silicon dioxide nano particle of non-surface-active agent synthesis
Method, the method is simple, and the Nano particles of silicon dioxide being obtained has 20～50 nanometers of ultra-small grain size, this nano-particle
Aperture is 1～2 nanometer, and inside has abundant pore structure, has good biocompatibility and biodegradability, can
It is applied to biomedicine field as a kind of anti-cancer medicament carrier.
For reaching this purpose, the present invention employs the following technical solutions:
On the one hand, the invention provides a kind of preparation method of mesoporous silicon dioxide nano particle, methods described is: by ammonia
The polyglycidyl ether absorption silica precursor of base functionalization, hydrolyzes afterwards, then through separation of solid and liquid, washs, be dried and obtain
Mesoporous silicon dioxide nano particle.
The preparation method of mesoporous silicon dioxide nano particle that the present invention provides passes through silica precursor and amino work(
Polyglycidyl ether (the pg-nh of energyization2) suction-operated, one kettle way synthesizing mesoporous silicon dioxide nanoparticle under hydrolysising condition
Son.The synthetic method of mesoporous silicon dioxide nano particle that the present invention provides is simple, does not use surfactant in course of reaction,
Reaction condition is gentle, and cost is relatively low.
Silica precursor of the present invention is to hydrolyze the material obtaining silica, typical but non-limiting
Have in tetraethyl orthosilicate, positive silicic acid propyl ester or positive isopropyl silicate any one or at least two mixture.
Preferably, described silica precursor is tetraethyl orthosilicate (teos).
Preferably, the amino functional degree of described polyglycidyl ether is 5～50%, such as 6%, 10%, 15%,
18%th, 20%, 25%, 30%, 35%, 40%, 45% or 48%.
Described amino functional degree refers to that the hydroxyl being replaced by amino in polyglycidyl ether accounts for the ratio of total hydroxyl.
Preferably, the weight average molecular weight of described polyglycidyl ether is 3000～20000, such as 3500,4000,5000,
6000th, 7000,8000,9000,10000,12000,13000,15000,17000 or 19000 etc..
Preferably, the polyglycidyl ether (pg-nh of described amino functional2) with the quality of described silica precursor
Ratio for 1:0.2～20, such as 1:0.3,1:0.5,1:0.8,1:1,1:1.5,1:2,1:3,1:4,1:6,1:8,1:10,1:12,1:
14th, 1:16 or 1:18 etc..Described mass ratio is different, and the particle diameter of mesoporous silicon dioxide nano particle preparing is different, particle diameter
Increase with the increase of the polyglycidyl ether mass ratio of amino functional with silica precursor, can be within 100 nanometers
Range regulation.
Described it is adsorbed as the polyglycidyl ether (pg-nh of amino functional2) and silica precursor be dissolved in solvent
In, carry out blending absorption.Described solvent is methyl alcohol and/or ethanol, and described methyl alcohol and/or ethanol play the described silica of dissolving
The effect of the polyglycidyl ether of presoma and described amino functional, its consumption according to described silica precursor with described
The quality of the polyglycidyl ether of amino functional is different and different, as long as can be by described silica precursor and described ammonia
The polyglycidyl ether of base functionalization dissolves.Described blending absorption is carried out in closed environment, the temperature of described blending absorption
Degree is preferably 15～30 DEG C, such as 16 DEG C, 18 DEG C, 20 DEG C, 22 DEG C, 25 DEG C, 26 DEG C, 27 DEG C, 28 DEG C or 29 DEG C etc., more preferably room
Temperature, adsorption time is preferably 2～48h, such as 3h, 4h, 5h, 10h, 15h, 18h, 20h, 23h, 25h, 28h, 30h, 33h, 35h,
38h, 40h, 43h or 45h etc..
Described hydrolysis is carried out in alkaline environment.
Preferably, described hydrolysis is carried out in the alkaline environment that ammoniacal liquor is adjusted；The volumetric concentration of described ammoniacal liquor is preferably 10
～50%, such as 12%, 15%, 18%, 20%, 23%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%,
45% or 48%.The volumetric concentration of described ammoniacal liquor is that the volume of ammoniacal liquor accounts for the ratio of reaction system volume.Described base catalyst
Add the hydrolysis being conducive to silica precursor.Described hydrolysis time is preferably 6～48h, such as 8h, 10h, 12h, 14h, 16h,
18h, 20h, 22h, 25h, 27h, 30h, 32h, 34h, 35h, 37h, 39h, 40h, 42h, 45h or 47h etc..
In described absorption and hydrolytic process, persistently it is stirred, described mixing speed is 500～2000rpm, such as 600,
800th, 900,1000,1200,1300,1400,1500,1600,1700,1800 or 1900 etc..
Described solid-liquid separation method is centrifugation or filtration separation.
On the other hand, the invention provides a kind of concrete grammar preparing mesoporous silicon oxide, comprise the steps:
(1) polyglycidyl ether of tetraethyl orthosilicate and amino functional is dissolved in organic solvent, carries out absorption 2 is blended
～48h, obtains reaction solution；
(2) add ammoniacal liquor in the described reaction solution of step (1), be 10～50% to its volumetric concentration, be hydrolyzed anti-
Answer 6～48h, obtain the sub- dispersion liquid of mesoporous silicon dioxide nano particle；
(3) by silica precursor dispersion liquid separation of solid and liquid, filter residue is scrubbed, after being dried, obtains mesoporous silicon oxide
Nano-particle.
Preferably, step (1) is: the polyglycidyl ether of tetraethyl orthosilicate and amino functional is filled in methanol solution
Divide the solution mixing to transparent clarification, be stirred overnight in closed container.
Preferably, step (2) is: by the mixed solution of ammoniacal liquor fast drop to step (1), and quickly stirs.
Preferably, step (3) is: by sub- for mesoporous silicon dioxide nano particle dispersion liquid centrifugation, and gained filter residue is used
Ethanol and water wash three times respectively, are dried to obtain mesoporous silicon dioxide nano particle.
Present invention also offers a kind of mesoporous silicon dioxide nano particle of utilization method as defined above preparation, described dioxy
The particle size of SiClx nano-particle is 20～50 nanometers, such as 22 nanometers, 25 nanometers, 28 nanometers, 30 nanometers, 32 nanometers, 35 receive
Rice, 38 nanometers, 40 nanometers, 42 nanometers, 45 nanometers or 48 nanometers etc., the hole of described Nano particles of silicon dioxide is received for 1～2
Rice.
Present invention also offers a kind of nano-particle loading medicine, described nano-particle is using method as defined above system
Standby mesoporous silicon dioxide nano particle, described medicine is the drug molecule of positive charge or the drug molecule of negative electrical charge.Described receive
Rice corpuscles is degradable in physiological saline, can be had ph sensitiveness by cell endocytic.
Present invention also offers a kind of purposes of the nano-particle of medicine loaded as described above, the nanometer of described loading medicine
Particle is used as anti-cancer medicament carrier or cell marking.The present invention provide mesoporous silicon dioxide nano particle due to good dispersion,
There is abundant nanoaperture, and there is good biocompatibility and biodegradability, can adsorb different charge respectively
The drug molecule of matter simultaneously discharges in weakly acidic condition, can be applied to biological doctor as anti-cancer medicament carrier or cell marking etc.
Medicine field.
Compared with prior art, the invention has the benefit that
(1) preparation method of mesoporous silicon dioxide nano particle that the present invention provides is simple: mesoporous silicon dioxide nano particle
Son is by silica precursor and pg-nh2Molecule is prepared by one kettle way under alkaline hydrolysis conditions, and product is passed through simple
Centrifuge washing method, it is to avoid the step of complicated harsh removing template in traditional preparation methods；
(2) present invention provide the sub- size controlling of mesoporous silicon dioxide nano particle within 100 nanometers, and can by control
Silica precursor and pg-nh2Mass ratio effectively regulate and control, this grain size is more suitable for nano-medicament carrier to be carried out
Antineoplaston；
(3) the sub pg molecular dopant compatible by having good biological of the mesoporous silicon dioxide nano particle that the present invention provides,
Thus this particle also shows good bio-compatibility and possesses biodegradability.
Brief description
Fig. 1 is the mesoporous silicon dioxide nano particle building-up process schematic diagram that the present invention provides；
Fig. 2 is the flying-spot microscope image of mesoporous silicon dioxide nano particle that particle diameter prepared by embodiment 1 is 50 nanometers
(a) and images of transmissive electron microscope (b)；
Fig. 3 is the transmission electron microscope image (a) of mesoporous silicon dioxide nano particle of embodiment 1 preparation, n element divides
Cloth analysis (b) and si element distribution analysis (c)；
Fig. 4 be embodiment 1 preparation mesoporous silicon dioxide nano particle load anticancer drugs, doxorubicin after in different ph values
Under the conditions of cushioning liquid in release profiles: ■ is the release profiles in the mes of ph=5.0；▲ it is ph=7.2's
Release profiles in pbs；
Fig. 5 is different time under the conditions of 37 DEG C in physiological saline of mesoporous silicon dioxide nano particle prepared by embodiment 1
Transmission electron microscope picture after the degradation behavior of section and different time sections degraded；
Fig. 6 be embodiment 1 preparation mesoporous silicon dioxide nano particle load anticancer drugs, doxorubicin after with tumour cell
Hela act on 3 hours after laser confocal scanning image；
Fig. 7 is that mesoporous silicon dioxide nano particle of embodiment 1 preparation loads the dyestuff rose with adriamycin opposite charges
After bengal, the release profiles in different cushioning liquid: ■ is the release profiles in the mes of ph=5.0；▲ it is in ph=
Release profiles in 7.2 pbs；
Before Fig. 8 is the anticancer drugs, doxorubicin of mesoporous silicon dioxide nano particle loading various dose of embodiment 1 preparation
Study of cytotoxicity to tumour cell hela afterwards；
Fig. 9 is (pg-nh under the conditions of different ratios of raw materials2: teos, weight ratio) prepare mesoporous silicon dioxide nano particle
Transmission electron microscope picture: a) 0:8, b) 1:0.8, c) 1:4, d) 1:8, e) 1:16, f) 1:16 (reaction dissolvent is 4 times of condition e).
Specific embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by specific embodiment.
Those skilled in the art understand the present invention it will be clearly understood that described embodiment is only used for help, are not construed as to this
Bright concrete restriction.
Fig. 1 is the mesoporous silicon dioxide nano particle synthesis schematic diagram that the present invention provides.Described synthesis step is:
(1) teos and pg-nh2Blending absorption in methanol solution；
(2) ammonia spirit is added in the mixed solution of (1), be hydrolyzed reaction, obtains mesoporous silicon oxide dispersion liquid；
(3) by mesoporous silicon oxide dispersion liquid centrifugation, then wash, be dried to obtain mesoporous silicon dioxide nano particle.
Embodiment 1
Prepare mesoporous silicon dioxide nano particle:
(1) adsorb: take pg methanol solution 600 μ l (pg weight average molecular weight about 10,000, the amino functional journey of amino functional
Degree 30%, its concentration of methanol solution 20mg/ml), add 2ml methyl alcohol and 100 μ lteos (control pg-nh2Quality with teos
Than for 1:8), it is stirred together under the stirring condition of 1000rpm in room temperature closed container 12 hours, obtain reaction solution.
(2) hydrolyze: rapidly join 1.5ml ammoniacal liquor and 1.5ml water in above-mentioned reaction solution, in the stirring bar of 1800rpm
React 6 hours under part, obtain the sub- dispersion liquid of mesoporous silicon dioxide nano particle；
(3) post-process: the mesoporous silicon dioxide nano particle dispersion being obtained with supercentrifuge step with centrifugal separation (2)
Liquid, and use methyl alcohol and water washing 3 times respectively, it is dried, obtain mesoporous silicon dioxide nano particle.
Structural characterization and performance test:
Using SEM (hitachi s-4800) and transmission electron microscope (philips tecnai g2
F20ut) to embodiment 1 be obtained mesoporous silicon dioxide nano particle carry out Micro-Structure Analysis (sample in advance through vacuum do
Dry), (Fig. 2 is the flying-spot microscope image and thoroughly of mesoporous silicon dioxide nano particle manufactured in the present embodiment to test result such as Fig. 2
Penetrate sem image) shown in；From figure 2 it can be seen that mesoporous silicon dioxide nano particle preparing has 50 ran
Ultra-small grain size, and there is inside it abundant loose structure.
Meso-porous titanium dioxide embodiment 1 being obtained using transmission electron microscope (philips tecnai g2 f20ut)
Silicon nano carries out element distribution analysis, and (Fig. 3 is mesoporous silicon dioxide nano manufactured in the present embodiment to test result such as Fig. 3
The transmission electron microscope image of particle and its element distribution analysis figure) shown in, it is derived from titanium dioxide as we can clearly see from the figure
The element silicon distribution of silicon, and the nitrogen distribution from amination pg molecule.
Fig. 4 be embodiment 1 preparation mesoporous silicon dioxide nano particle load anticancer drugs, doxorubicin after in different ph values
Under the conditions of cushioning liquid in release profiles: wherein MES (mes) buffer solution ph value is 5.0, phosphate (pbs)
Buffer solution ph value is 7.2, and drug loading efficiency is 0.238mg ADMh (dox)/mg sio2；It can be seen that drug molecule is in weak acid
Property under the conditions of can from mesoporous silicon dioxide nano particle discharge faster, show that this load powder has certain ph quick
Perception.
Fig. 5 is different time under the conditions of 37 DEG C in physiological saline of mesoporous silicon dioxide nano particle prepared by embodiment 1
Transmission electron microscope (philips tecnai g2 f20ut) picture after the degradation behavior of section and different time sections degraded, shows
Under the conditions of 37 DEG C, this particle solution (this is tested as 0.1mg/ml) of low concentration in pbs, gradually destroy by structure, has certain
Degradation behavior.
Fig. 6 is that mesoporous silicon dioxide nano particle of embodiment 1 preparation is mounted with rear mesoporous the two of anticancer drugs, doxorubicin
Silicon oxide nanoparticle and tumour cell hela act on 3 hours after laser co-focusing (olympus fv1000) scan image.
Experiment condition is: cell, after 35mm culture dish reaches exponential phase, adds 50 μ l to be dispersed in the sio in pbs2- dox solution
(1mg/ml, dox useful load is 0.18mg dox/mg sio2), after cultivating 3 hours, cell uses hoechst 33342 He respectively
Alexa 488wga dyes, and obtains nuclear image (a), the image (b) of cell membrane, sio2- dox distribution in the cell
The superimposed image (d) of (c) and abc.Show that this material is easy to, by cell endocytic, cancer therapy drug is loaded into inside tumor.
Fig. 7 is dyestuff rose bengal (rb) of the mesoporous silicon dioxide nano particle loading negative electrical charge of embodiment 1 preparation
Release profiles in different cushioning liquid afterwards, drug loading efficiency is 0.16mg rb/mg sio2, other experiment conditions are with loading
The sio of dox2Release conditions in pbs or mes.Show this nano-particle not only can adsorb positive charge adriamycin it is also possible to
The drug molecule of absorption negative electrical charge, and show similar release behavior.
Before Fig. 8 is the anticancer drugs, doxorubicin of mesoporous silicon dioxide nano particle loading various dose of embodiment 1 preparation
Study of cytotoxicity to tumour cell hela afterwards.Experiment condition is: hela cell reaches logarithmic growth in 96 well culture plates
After phase, every four holes are divided into 1 group, are separately added into 10,30,60,90,120 μ l dox-sio by group2Dispersion liquid (1mg/ml, dox
Charging ratio is 0.12mg dox/mg sio2)；10、30、60、90、120μl sio2Dispersion liquid (1mg/ml) and 10ul dox solution
(1mg/ml) cell after being loaded uses mtt method test cell toxicity after 24 hours.Without carried anticancer medicine compared with blank control group
Mesoporous silicon dioxide nano particle of thing has good cell compatibility, and after loading adriamycin, this particle is to hela cell table
Reveal obvious cytotoxicity, there is in terms of antineoplaston potential using value.
Embodiment 2
The method preparing mesoporous silicon dioxide nano particle is same as Example 1, and difference is, the addition of teos is
10 μ l, control pg-nh2Mass ratio with teos is 1:0.8.
Embodiment 3
The method preparing mesoporous silicon dioxide nano particle is same as Example 1, and difference is, the addition of teos is
50 μ l, control pg-nh2Mass ratio with teos is 1:4.
Embodiment 4
The method preparing mesoporous silicon dioxide nano particle is same as Example 1, and difference is, the addition of teos is
200 μ l, control pg-nh2Mass ratio with teos is 1:16.
Embodiment 5
The method preparing mesoporous silicon dioxide nano particle is same as Example 4, and difference is, the volume of reaction dissolvent
For solvent volume in embodiment 4 four times.
Embodiment 6
The method preparing mesoporous silicon dioxide nano particle is same as Example 1, and difference is, step is not added with (1)
Enter pg-nh2.
Mesoporous dioxy embodiment 1～6 being obtained using transmission electron microscope (philips tecnai g2f20ut)
It is as shown in Figure 9 that SiClx nano-particle carries out structural characterization.Fig. 9 is different ratios of raw materials condition (pg-nh2: teos, weight compares w/
The transmission electron micrograph of mesoporous silicon dioxide nano particle of preparation under w): a) 0:8, b) 1:0.8, c) 1:4, d) 1:8,
E) 1:16, f) 1:16 (reaction dissolvent is 4 times of condition e).It can be seen that without pg-nh2Prepared mesoporous dioxy
SiClx particle diameter is larger, pg-nh2And the mesoporous silicon oxide particle diameter of teos one kettle way preparation is between 20～50 nanometers, and more
Change pg-nh2Form and the particle diameter of particle can be regulated and controled with the mass ratio of teos within the specific limits.
Embodiment 7
Prepare mesoporous silicon dioxide nano particle:
(1) adsorb: take pg methanol solution 600 μ l (pg weight average molecular weight about 3000, the amino functional journey of amino functional
Degree 50%, its concentration of methanol solution 20mg/ml), add 2ml methyl alcohol and 25 μ lteos (control pg-nh2Quality with teos
Ratio is for 1:0.2), in 15 DEG C of closed containers, 500rpm stirs 2 hours, obtains reaction solution.
(2) hydrolyze: rapidly join 1.5ml ammoniacal liquor and 10.9ml water in above-mentioned reaction solution, in 500rpm stirring condition
Lower reaction 24 hours, obtains the sub- dispersion liquid of mesoporous silicon dioxide nano particle；
(3) post-process: the mesoporous silicon dioxide nano particle dispersion being obtained with supercentrifuge step with centrifugal separation (2)
Liquid, and use methyl alcohol and water washing 3 times respectively, it is dried, obtain particle diameter and be 50 nanometers, aperture is that 1 nanometer of mesoporous silicon oxide is received
Rice corpuscles.
Embodiment 8
Prepare mesoporous silicon dioxide nano particle:
(1) adsorb: take pg methanol solution 600 μ l (pg weight average molecular weight about 20,000, the amino functional journey of amino functional
Degree 5%, its concentration of methanol solution 20mg/ml), add 2ml methyl alcohol and 250 μ l teos (control pg-nh2Quality with teos
Ratio is for 1:20), in 30 DEG C of closed containers, 2000rpm stirs 48 hours, obtains reaction solution.
(2) hydrolyze: rapidly join 4.3ml ammoniacal liquor and 1.5ml water in above-mentioned reaction solution, in 2000rpm stirring condition
Lower reaction 48 hours, obtains the sub- dispersion liquid of mesoporous silicon dioxide nano particle；
(3) post-process: the mesoporous silicon dioxide nano particle dispersion being obtained with supercentrifuge step with centrifugal separation (2)
Liquid, and use methyl alcohol and water washing 3 times respectively, it is dried, obtain particle diameter and be 20 nanometers, aperture is that 2 nanometers of mesoporous silicon oxide is received
Rice corpuscles.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The interpolation of the equivalence replacement to each raw material of product of the present invention and auxiliary element, selection of concrete mode etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (19)
1. a kind of preparation method of mesoporous silicon dioxide nano particle is it is characterised in that methods described is: by amino functional
Polyglycidyl ether adsorbs silica precursor, hydrolyzes afterwards in alkaline environment, then through separation of solid and liquid, washs, and drying obtains
Obtain mesoporous silicon dioxide nano particle.
2. preparation method according to claim 1 is it is characterised in that described silica precursor is tetraethyl orthosilicate.
3. preparation method according to claim 1 is it is characterised in that the polyglycidyl ether of described amino functional is ammonia
Base functionalization degree is 5～50% polyglycidyl ether.
4. preparation method according to claim 1 is it is characterised in that the polyglycidyl ether of described amino functional and institute
The mass ratio stating silica precursor is 1:0.2～20.
5. preparation method according to claim 1 is it is characterised in that the weight average molecular weight of described polyglycidyl ether is
3000～20000.
6. preparation method according to claim 1 is it is characterised in that described be adsorbed as will be sweet for the bunching water of amino functional
Oily ether and silica precursor are dissolved in solvent, carry out blending absorption.
7. preparation method according to claim 6 is it is characterised in that described solvent is methyl alcohol and/or ethanol.
8. preparation method according to claim 6 is it is characterised in that described blending absorption is carried out in closed environment.
9. preparation method according to claim 6 it is characterised in that described blending absorption temperature be 15～30 DEG C, when
Between be 2～48h.
10. preparation method according to claim 1 is it is characterised in that described hydrolysis is in the alkaline environment that ammoniacal liquor is adjusted
Carry out.
11. preparation methods according to claim 10 are it is characterised in that the volumetric concentration of described ammoniacal liquor is 10～50%.
12. preparation methods according to claim 1 are it is characterised in that the time of described hydrolysis is 6～48h.
13. preparation methods according to claim 1 are it is characterised in that in described absorption and hydrolytic process, persistently stirred
Mix, described mixing speed is 500～2000rpm.
14. preparation methods according to claim 1 are it is characterised in that described solid-liquid separation method is centrifugation or mistake
Filter separates.
15. preparation methods according to one of claim 1-14 are it is characterised in that the method comprising the steps of:
(1) polyglycidyl ether of tetraethyl orthosilicate and amino functional is dissolved in organic solvent, carry out being blended absorption 2～
48h, obtains reaction solution；
(2) add ammoniacal liquor in the described reaction solution of step (1), be 10～50% to its volumetric concentration, the reaction 6 of being hydrolyzed～
48h, obtains the sub- dispersion liquid of mesoporous silicon dioxide nano particle；
(3) by silica precursor dispersion liquid separation of solid and liquid, filter residue is scrubbed, after being dried, obtains mesoporous silicon dioxide nano
Particle.
Mesoporous silicon dioxide nano particle of the method preparation described in a kind of one of 16. utilization claims 1-14, its feature exists
In the particle size of described Nano particles of silicon dioxide is 20～50 nanometers, and pore size is 1～2 nanometer.
17. a kind of nano-particle loading medicine is it is characterised in that described nano-particle is mesoporous two described in claim 16
Silicon oxide nanoparticle, described medicine is the drug molecule of positive charge or the drug molecule of negative electrical charge.
18. nano-particles loading medicine according to claim 17 are it is characterised in that described nano-particle is in physiology salt
Degradable in water, ph sensitiveness can be had by cell endocytic.
A kind of 19. purposes of the nano-particle loading medicine according to claim 17 are it is characterised in that described loading medicine
The nano-particle of thing is used as anti-cancer medicament carrier or cell marking.
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| CN107140652A (en) * | 2017-05-27 | 2017-09-08 | 中山大学 | Azide mesoporous silica nano-particle and preparation method thereof |
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| CN105106956B (en) * | 2015-08-17 | 2019-01-15 | 国家纳米科学中心 | A kind of mesoporous silicon dioxide nano particle and its preparation method and application with two-photon absorption function |
| CN110152018A (en) * | 2019-05-20 | 2019-08-23 | 上海大学 | The method of extra small fluorescent silicon dioxide nano particle carrier band adriamycin |
| CN111557306B (en) * | 2020-05-21 | 2021-05-18 | 中国热带农业科学院南亚热带作物研究所 | Nano-drug preparation and application thereof in prevention and control of banana vascular wilt |
| CN115160624B (en) * | 2022-07-15 | 2023-06-16 | 华南理工大学 | Food antibacterial preservative film with bacteria detection capability and preparation method thereof |
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| CN102145896A (en) * | 2010-02-08 | 2011-08-10 | 中国科学院过程工程研究所 | Superparamagnetism silicon dioxide mesoporous nanoparticle with three-dimensional mesoporous channel and preparation method thereof |
| US20110256184A1 (en) * | 2010-04-14 | 2011-10-20 | Battelle Memorial Institute | Non-ordered Mesoporous Silica Structure for Biomolecule Loading and Release |
| CN102786061B (en) * | 2012-07-20 | 2014-01-29 | 东华大学 | Preparation method of hollow mesoporous silica nanoparticle |
| CN103787344B (en) * | 2012-10-31 | 2016-08-03 | 国家纳米科学中心 | A kind of water solublity mesoporous monox nanometer granule and its production and use |
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2015
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107140652A (en) * | 2017-05-27 | 2017-09-08 | 中山大学 | Azide mesoporous silica nano-particle and preparation method thereof |
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